Preparation of ZrO2-Al2O3 composite carrier by precipitation method and preliminary study on its catalytic performance in methanation
WU Gang-qiang1,2, LANG Zhong-min1, WANG Ya-xiong1, XU Shao-ping2
1. School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou 014010, China; 2. School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
Abstract: A porous ZrO2-Al2O3 composite carrier is synthesized by a precipitation method using a mixed solution of zirconium oxychloride and aluminum nitrate as a precursor,ammonia as a precipitant and PEG-6000 as a dispersant.The effects of the concentration of mixed solution,the molar ratio of zirconium to aluminum,the dosage of dispersant and the roasting time on the specific surface area of porous ZrO2-Al2O3 composite carrier are investigated by orthogonal experiment.The optimal process conditions for the synthesis of porous ZrO2-Al2O3 composite carrier are obtained by orthogonal analysis as follows:the concentration of mixed solution is 0.4 mol·L-1,the molar ratio of zirconium to aluminum is 3∶7,the dosage of dispersant (polyethylene glycol-6000) is 1 g,and the roasting time is 6 hours.ZrO2-Al2O3 composite carrier synthesized under the optimum conditions is characterized by BET,SEM,XRD and particle size analysis.The results show that the synthesized ZrO2-Al2O3 composite carrier has small particle size,uniform particle size distribution,loose surface and large specific surface area,and is suitable as a carrier for supporting catalysts.Ni/ZrO2-Al2O3 catalyst is prepared through impregnation method by loading Ni and its catalytic activity for methanation is preliminarily detected.It is found that the conversion rate of CO over the catalyst increases monotonically with increasing temperature,reaching 89% at 470℃,and decreases then.CH4 selectivity also has a similar variation pattern,reaching 98% at 470℃.
吴刚强, 郎中敏, 王亚雄, 徐绍平. 沉淀法ZrO2-Al2O3复合载体的制备及其甲烷化催化性能初探[J]. 现代化工, 2020, 40(2): 110-113.
WU Gang-qiang, LANG Zhong-min, WANG Ya-xiong, XU Shao-ping. Preparation of ZrO2-Al2O3 composite carrier by precipitation method and preliminary study on its catalytic performance in methanation. Modern Chemical Industry, 2020, 40(2): 110-113.
 杨喜锐.二氧化锆纳米粉体和涂层的制备及性能研究[D].大连:大连理工大学,2017.  王志,刘恩利,左满宏,等.超细二氧化锆制备与表征[J].工业催化,2008,5(29):22759-22776.  王晶,许吉泰,龚念.水热法制备球形二氧化锆粉体的研究[J].硅酸盐通报,2013,32(5):936-940.  Christian M Pichler,Dong Gu,Hrishikesh Joshi,et al.Influence of preparation method and doping of zirconium oxide onto the material characteristics and catalytic activity for the HDO reaction in nickel on zirconium oxide catalysts[J].Journal of Catalysis,2018,365:367-375.  Liu Qihai,Dong Xinfa,Liu Zili.Performance of Ni/Nano-ZrO2 catalysts for CO preferential methanation[J].Chin J Chem Eng,2014,22(2):131-135.  Li Zhenhua,Tian Ye,He Jia,et al.High CO methanation activity on zirconia-supported molybdenum sulfide catalyst[J].Journal of Energy Chemistry,2014,23(5):625-632.  Huang Yanhui,Wang Jijie,Liu Zhiming,et al.Highly efficient Ni-ZrO2 catalyst doped with Yb2O3 for co-methanation of CO and CO2[J].Applied Catalysis A:General,2013,466:300-306.  Liu Qihai,Dong Xinfa,Mo Xinman,et al.Selective catalytic methanation of CO in hydrogen-rich gases over Ni/ZrO2 catalyst[J].Journal of Natural Gas Chemistry,2008,17:268-272.  姚玉芹,刘思含,胡宗元,等.γ-Al2O3性质对钼基耐硫甲烷化催化剂活性的影响[J].石油化工,2014,43(7):754-758.  杨霞,郑文涛,汪国高,等.MgO对Ni/Al2O3催化剂CO甲烷化性能的影响[J].现代化工,2014,34(1):90-94.  王宁,孙自瑾,王永钊,等.Ni-Fe/γ-Al2O3双金属催化剂的制备及其CO甲烷化性能研究[J].燃料化学学报,2011,39(3):219-223.  Qin Hongyun,Guo Cuili,Wu Yuanyuan,et al.Effect of La2O3 promoter on NiO/Al2O3 catalyst in CO methanation[J].Korean J Chem Eng,2014,31(7):1168-1173.  Guo Cuili,Wu Yuanyuan,Qin Hongyun,et al.CO methanation over ZrO2/Al2O3 supported Ni catalysts:A comprehensive study[J].Fuel Processing Technology,2014,124:61-69.  舒展霞.二氧化锆纳米材料的水热溶剂热法控制合成级性质表征[D].济南:山东大学,2012.